EP3285324B1 - Électrolyte polymère à structure multicouche, et batterie tout solide le comprenant - Google Patents

Électrolyte polymère à structure multicouche, et batterie tout solide le comprenant Download PDF

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EP3285324B1
EP3285324B1 EP16860299.3A EP16860299A EP3285324B1 EP 3285324 B1 EP3285324 B1 EP 3285324B1 EP 16860299 A EP16860299 A EP 16860299A EP 3285324 B1 EP3285324 B1 EP 3285324B1
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polymer electrolyte
lithium
solid battery
solid
polymer
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EP3285324A1 (fr
EP3285324A4 (fr
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Dong Wook Ko
Doo Kyung Yang
Eun Kyung Park
Jong Hyun Chae
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LG Chem Ltd
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LG Chem Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0568—Liquid materials characterised by the solutes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0082—Organic polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0088—Composites
    • H01M2300/0094—Composites in the form of layered products, e.g. coatings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/497—Ionic conductivity
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a polymer electrolyte with a multi-layer structure for an all-solid-state battery and, more particularly, to a polymer electrolyte having a multi-layer structure, which comprises a first polymer electrolyte layer and a second polymer electrolyte layer, wherein the EO : Li molar ratio of a poly(ethylene oxide)(PEO)-based polymer and a lithium salt is different between the first and second polymer electrolyte layers.
  • secondary batteries particularly lithium-based secondary batteries have higher capacity density than other secondary batteries and can operate at higher voltages, and thus are used for information-related devices or communication devices as secondary batteries for miniaturization and light weight. Recently, the development of high power and high capacity lithium-based secondary batteries for electric vehicles or hybrid vehicles is underway.
  • a typical lithium-based secondary battery consists of a positive electrode (cathode), a negative electrode (anode) and an electrolyte containing lithium salt interposed therebetween, and this electrolyte may be a non-aqueous liquid electrolyte or a solid electrolyte.
  • this electrolyte may be a non-aqueous liquid electrolyte or a solid electrolyte.
  • the lithium-based secondary battery uses a flammable organic solvent in the liquid electrolyte, in order to prevent ignition or rupture that may occur due to over current caused by short, it may be necessary to install a safety device. In addition, in order to prevent such a phenomenon, there are cases where the selection of the battery material or the design of the battery structure is restricted.
  • the all-solid battery since the all-solid battery does not contain a flammable organic solvent, the all-solid battery has the advantage of simplifying the safety device and thus is recognized as a superior battery in terms of manufacturing cost or productivity.
  • the all-solid battery since it is easy to laminate, in series, a pair of electrode layers including a positive electrode (cathode) layer and a negative electrode (anode) layer, and a junction structure including a solid electrolyte layer lying between these electrode layers, the all-solid battery is expected to be a technology capable of producing a high-capacity and high-output battery with stability.
  • LiNbO3 -coated LiCoO2 as cathode material for all solid-state lithium secondary batteries LiNbO 3 (lithium niobate) is described as a material to be coated on the surface of LiCoO 2 (positive electrode active material).
  • This technique aims to obtain a high-power battery in such a manner that the surface of the LiCoO 2 is coated with LiNbO 3 to suppress the reaction between LiCoO 2 and the solid electrolyte material, thereby reducing the interfacial resistance between LiCoO 2 and the solid electrolyte material.
  • Japanese Laid-Open Patent Publication No. 2004-206942 discloses an all-solid battery wherein a second solid electrolyte layer, which does not chemically react with the first solid electrolyte and has lower ion conductivity than the first solid electrolyte layer (sulfide based solid electrolyte material), is formed between the first solid electrolyte layer and a negative electrode made of metal lithium. This application attempts to inhibit the reaction between the first solid electrolyte layer and the metal lithium through formation of the second solid electrolyte layer with low ion conductivity.
  • the all-solid battery to which a solid polymer electrolyte was applied is difficult to exhibit sufficient output or capacity even at room temperature, as well as at 60 ⁇ or 80 ⁇ . For this reason, first, the low ionic conductivity of the polymer electrolyte and second, the interfacial resistance between lithium and the polymer electrolyte can be mentioned. Many efforts have been made to solve the ion conductivity of the polymer electrolyte in the interim, but there was no remarkable improvement in ion conductivity and it has been pointed out as a limitation of the solid polymer electrolyte.
  • the present inventors in view of this, have come to complete the present invention by applying a polymer electrolyte using a high concentration of lithium salt to the all-solid battery to lower the interfacial resistance between lithium and the solid polymer electrolyte.
  • the purpose of the present invention is to provide a polymer electrolyte for the all-solid battery, which significantly reduces the interfacial resistance between lithium and the polymer electrolyte.
  • the present invention provides a polymer electrolyte with multi-layer structure for an all-solid battery, which comprises a first polymer electrolyte layer having a molar ratio of EO : Li of poly (ethylene oxide) (PEO) -based polymer and lithium salt of 1 : 1 to 7 : 1; and a second polymer electrolyte layer having a molar ratio of EO : Li of poly (ethylene oxide) - based polymer and lithium salt of 8 : 1 to 30 : 1.
  • the thickness of the first polymer electrolyte layer may be 1 to 5 ⁇ m.
  • the thickness of the second polymer electrolyte layer may be 5 to 50 ⁇ m.
  • the weight average molecular weight (Mw) of the poly (ethylene oxide) -based polymer may be 1,000,000 to 8,000,000.
  • the lithium salt may include one selected from the group consisting of LiCl, LiBr, LiI, LiClO 4 , LiBF 4 , LiB 10 Cl 10 , LiPF 6 , LiCF 3 SO 3 , LiCF 3 CO 2 , LiAsF 6 , LiSbF 6 , LiAlCl 4 , CH 3 SO 3 Li, CF 3 SO 3 Li, LiSCN, LiC(CF 3 SO 2 ) 3 , (CF 3 SO 2 ) 2 NLi, (FSO 2 ) 2 NLi, chloroborane lithium, lithium lower aliphatic carboxylate, lithium tetraphenylborate, lithium imide, and combinations thereof.
  • the second polymer electrolyte layer may be crosslinked by a crosslinking monomer to form semi-Interpenetrating Polymer Networks (semi-IPN).
  • the crosslinking monomer may contain -(CH 2 -CH 2 -O)-repeating units.
  • the crosslinking monomer may contain 2 to 8 alkylenic unsaturated bonds at the terminals.
  • the crosslinking monomer may be contained in an amount of 5 to 50 wt.% relative to the poly (ethylene oxide)-based polymer and lithium salt.
  • the present invention also provides an all-solid battery comprising a positive electrode, a negative electrode and a solid polymer electrolyte interposed therebetween, characterized in that the solid polymer electrolyte is the polymer electrolyte with the multi-layer structure for the all-solid battery.
  • the first polymer electrolyte layer may be disposed facing the negative electrode.
  • the solid polymer electrolyte of the present invention When the solid polymer electrolyte of the present invention is applied to the all-solid battery, the interfacial resistance with lithium and the discharge overvoltage are significantly reduced, thereby resulting in sufficient discharge capacity and improving output characteristics and energy density.
  • the polymer electrolyte of the present invention applicable to the all-solid battery as the lithium secondary battery is a polymer electrolyte with a multilayer structure, comprising a first polymer electrolyte layer and a second polymer electrolyte layer which include poly (ethylene oxide) (PEO)-based polymer and lithium salt and are different in EO : Li molar ratios of the poly (ethylene oxide)-based polymer and lithium salt.
  • PEO poly (ethylene oxide)
  • the first polymer electrolyte layer is applied to lower the interfacial resistance and is prepared by selecting the molar ratio of EO : Li of poly (ethylene oxide) -based polymer and lithium salt within the range of 1 : 1 to 7 : 1.
  • EO Li of poly (ethylene oxide) -based polymer
  • lithium salt when lithium salt is doped at a high ratio and accordingly thinned to a thickness of 1 to 5 ⁇ m, the ionic conductivity is somewhat lowered, but the interfacial resistance can be significantly lowered.
  • the second polymer electrolyte layer is applied to prevent the phenomenon due to the generation of dendrite by increasing the mechanical strength, and is prepared by selecting the molar ratio of EO : Li of poly (ethylene oxide)-based polymer and lithium salt within the range of 8 : 1 to 30 : 1. At this time, the thickness of the second polymer electrolyte layer may be 5 to 50 ⁇ m.
  • the second polymer electrolyte layer may be crosslinked by a crosslinking monomer to form a semi-Interpenetrating Polymer Networks (hereinafter, referred to as semi-IPN) structure.
  • This semi-IPN structure can increase the strength of the solid polymer electrolyte and, as the strength is high, the generation of lithium dendrite on the surface of the electrode can be physically suppressed.
  • Mw weight average molecular weight
  • the poly (ethylene oxide)-based polymer is applied in a relatively high molecular weight in the range of 1,000,000 to 8,000,000, a more compact semi-IPN structure can be formed.
  • a crosslinking monomer a polyfunctional monomer having two or more functional groups can be used, and such monomer preferably contains -(CH 2 -CH 2 -O)- repeating units and polymerizable alkylenic unsaturated bonds in the range of 2 to 8 at both terminals.
  • the alkylenic unsaturated bond is a hydrocarbon group containing at least one carbon-carbon double bond or triple bond, and includes, but not limited to, ethenyl group, 1-propenyl group, 2-propenyl group, 2-methyl-1-propenyl group, 1-butenyl group, 2-butenyl group, ethynyl group, 1-propynyl group, 1-butynyl group, 2-butynyl group and the like.
  • These alkylenic unsaturated bonds act as crosslinking points to crosslink the poly (ethylene oxide) -based polymer through a polymerization process, thereby forming a semi-IPN structure.
  • the crosslinking monomer may be selected from the group consisting of polyethylene glycol diacrylate (PEGDA), polyethylene glycol dimethacrylate (PEGDMA), poly (propylene glycol) diacrylate : PPGDA), poly (propylene glycol) dimethacrylate (PPGDMA), and combinations thereof, and preferably, polyethylene glycol diacrylate (PEGDA) can be used.
  • PEGDA polyethylene glycol diacrylate
  • PEGDMA polyethylene glycol dimethacrylate
  • PPGDA poly (propylene glycol) diacrylate
  • PPGDMA poly (propylene glycol) dimethacrylate
  • PEGDA polyethylene glycol diacrylate
  • the crosslinking monomer is preferably contained in an amount of 5 to 50 wt.% relative to the weight of the poly (ethylene oxide)-based polymer to form a semi-IPN structure meeting the object of the present invention.
  • crosslinking the crosslinking monomer between the poly (ethylene oxide)-based polymers there is no particular limitation on the method of crosslinking the crosslinking monomer between the poly (ethylene oxide)-based polymers, but preferably the crosslinking monomer can be crosslinked while maintaining a proper temperature condition after adding a thermal initiator. At this time, it is possible to apply benzoyl peroxide (BPO) or azobisisobutyronitrile (AIBN) as a thermal initiator.
  • BPO benzoyl peroxide
  • AIBN azobisisobutyronitrile
  • the lithium salt which is commonly applied to the first polymer electrolyte layer and the second polymer electrolyte layer according to the present invention, can be dissociated into lithium ions and can permeate into the first polymer electrolyte layer and the second polymer electrolyte layer to move freely.
  • the basic operation of the lithium battery is possible by the source of lithium ions, and these lithium salts can be used as long as they are commonly used in lithium batteries, and preferably, the lithium salt includes LiCl, LiBr, LiI, LiClO 4 , LiBF 4 , LiB 10 Cl 10 , LiPF 6 , LiCF 3 SO 3 , LiCF 3 CO 2 , LiAsF 6 , LiSbF 6 , LiAlCl 4 , CH 3 SO 3 Li, CF 3 SO 3 Li, LiSCN, LiC(CF 3 SO 2 ) 3 , (CF 3 SO 2 ) 2 NLi, (FSO 2 ) 2 NLi, chloroborane lithium, lithium lower aliphatic carboxylate, lithium tetraphenylborate, lithium imide, and combinations thereof, and more preferably, lithium bis(fluorosulfonyl) imide (LiFSI) represented by (FSO 2 ) 2 NLi can be used as the lithium salt.
  • LiFSI lithium
  • the method of preparing the first polymer electrolyte layer or the second polymer electrolyte layer of the present invention is not limited in the present invention, and the mixing and molding process by the wet or dry method as known in the art may be used. Also, the thickness of the solid polymer electrolyte of the present invention can be selected within the range of 1 to 50 ⁇ m.
  • An all-solid battery comprising the solid polymer electrolyte of the present invention interposed between the positive electrode and the negative electrode is described, wherein the first polymer electrolyte layer faces the negative electrode and the interfacial resistance is significantly reduced.
  • each electrode active material may be any active material applied to conventional electrodes, and is not particularly limited in the present invention.
  • the positive electrode or negative electrode active material used in the present invention varies depending on the type of conducting ions of the all-solid battery intended. For example, if the all-solid battery according to the present invention is an all-solid lithium secondary battery, the positive electrode or negative electrode active material occludes or releases lithium ions. In addition, the positive electrode or negative electrode active material used in the present invention can typically react with the solid electrolyte material described above to form a high-resistance portion.
  • the positive electrode active material can be varied depending on the usage of the lithium secondary battery, and a known material is used for the specific composition.
  • such positive electrode active material may be any one of lithium transition metal oxides selected from the group consisting of lithium-phosphate-iron compound, lithium cobalt-based oxide, lithium manganese-based oxide, lithium copper oxide, lithium nickel-based oxide, lithium manganese composite oxide, and lithium-nickel-manganese-cobalt-based oxide.
  • the lithium metal phosphorous oxides represented by Li 1+a M(PO 4 - b )X b the lithium metal phosphorous oxides wherein M is at least one selected from the metals of Groups 2 to 12 and X is at least one selected from F, S and N, -0.5 ⁇ a ⁇ +0.5, and 0 ⁇ b ⁇ 0.1 are preferable.
  • the negative electrode active material can be one selected from the group consisting of lithium metal, lithium alloy, lithium metal composite oxide, lithium containing titanium composite oxide (LTO), and combinations thereof.
  • the lithium alloy may be an alloy of lithium and at least one metal selected from Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Ba, Ra, Al and Sn.
  • the lithium metal composite oxide may be a lithium metal composite oxide made of lithium and any one metal (Me) oxide (MeO x ) selected from the group consisting of Si, Sn, Zn, Mg, Cd, Ce, Ni and Fe, and as an example, may be Li x Fe 2 O 3 (0 ⁇ x ⁇ 1) or LixWO 2 ⁇ 0 ⁇ x ⁇ 1).
  • the conducting material is not particularly limited as long as it has electrical conductivity without causing a chemical change in the relevant battery, and for example, graphite; carbon black such as carbon black, acetylene black, ketjen black, channel black, furnace black, lamp black, and summer black; conductive fibers such as carbon fiber and metal fiber; metal powders such as carbon fluoride, aluminum, and nickel powder; conductive whisker such as zinc oxide and potassium titanate; conductive metal oxide such as titanium oxide; and conductive materials such as polyphenylene derivatives can be used.
  • graphite carbon black such as carbon black, acetylene black, ketjen black, channel black, furnace black, lamp black, and summer black
  • conductive fibers such as carbon fiber and metal fiber
  • metal powders such as carbon fluoride, aluminum, and nickel powder
  • conductive whisker such as zinc oxide and potassium titanate
  • conductive metal oxide such as titanium oxide
  • conductive materials such as polyphenylene derivatives can be used.
  • conductive materials include acetylene black based products of Chevron Chemical Company products or Denka products (Singapore Private Limited), Gulf Oil Company products, Ketjenblack, EC series Armak Company products, Vulcan XC-72 Cabot Company products and Super P (Timcal Company products).
  • the binder is a component that assists in binding of the active material and the conductive material etc. and binding to the current collector, and is usually added in an amount of 1 to 50 wt.% based on the total weight of the mixture containing the electrode active material.
  • An example of such binders includes polyvinylidene fluoride, polyvinyl alcohol, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, polyvinyl pyrrolidone, tetrafluoroethylene, polyethylene, polypropylene, ethylene-propylene-diene terpolymer (EPDM), sulfonated EPDM, styrene butylene rubber, fluorine rubber, various copolymers and the like.
  • the filler is not particularly limited as long as it is a fibrous material without causing chemical change in the relevant battery, and for example, include olefinic polymers such as polyethylene, polypropylene and the like; and fibrous materials such as glass fibers, carbon fibers and the like.
  • a high resistance portion is created at the interface between the electrode active material and the solid a polymer electrolyte material. Accordingly, when the first polymer electrolyte layer and the second polymer electrolyte layer according to the present invention are used to form the all-solid battery, it is possible to reduce the interfacial resistance to the movement of the ions across the interface between the electrode active material and the solid electrolyte material, thereby suppressing the reduction in the output.
  • the first polymer electrolyte layer is disposed facing the negative electrode, the second polymer electrolyte layer is formed thereon, and the positive electrode is formed thereon. If the stacking order of the first and second polymer electrolyte layers is reversed, it is undesirable because the resistance of the battery may increase and thus the discharge capacity may decrease.
  • two polymer electrolyte layers having different EO Li molar ratios of the poly (ethylene oxide)-based polymer and lithium salt, i.e. to simultaneously apply the first polymer electrolyte layer having the molar ratio of EO : Li of the poly (ethylene oxide)-based polymer and the lithium salt of 1 : 1 to 7 : 1 and the second polymer electrolyte layer having the molar ratio of EO : Li of poly (ethylene oxide)-based polymer and lithium salt of 8 : 1 to 30 : 1.
  • the first polymer electrolyte layer is out of the above range, it is undesirable because the interfacial resistance may increase and thus the discharge capacity may decrease, and if the second polymer electrolyte layer is out of the above range, it is undesirable because the resistance of the electrolyte-separation membrane layer may increase and thus the discharge capacity may decrease.
  • the all-solid battery is manufactured through a dry compression process in which electrodes and solid electrolytes are prepared in powder form, then charged into a given mold and then pressed, or a slurry coating process in which a slurry composition including an active material, a solvent, and a binder is prepared, then coated, and then dried.
  • the preparation of the all-solid battery having the above-described composition is not particularly limited in the present invention, and a known method can be used.
  • a cell is assembled by placing the solid electrolyte between the positive electrode and the negative electrode, and then compressing and molding them.
  • the assembled cell is installed in the exterior material and then sealed by heat compression or the like.
  • Laminate packs such as aluminum, stainless steel and the like, or cylindrical or square metal containers are very suitable for the exterior material.
  • the method of coating the electrode slurry on the current collector may include a method of distributing the electrode slurry over the current collector and then uniformly dispersing the slurry using a doctor blade or the like, and methods such as die casting, comma coating, screen printing and the like.
  • the electrode slurry may be bonded to the current collector by pressing or lamination method after forming on a separate substrate. At this time, the thickness of the coating to be finally coated can be adjusted by controlling the concentration of the slurry solution, the number of coatings or the like.
  • the drying process is a process for removing the solvent and moisture in the slurry in order to dry the slurry coated on the metal current collector, and may be changed depending on the solvent used.
  • the drying process is carried out in a vacuum oven at 50 to 200 ⁇ .
  • the drying method may include, for example, a drying method by warm air, hot air, or low-humidity air, vacuum drying, and a drying method by irradiation with (far-) infrared ray or electron beam.
  • the drying time is not particularly limited, but is usually carried out in the range of 30 seconds to 24 hours.
  • a cooling process may be further included, and the cooling process may be a process of slowly cooling to room temperature so that the recrystallized structure of the binder is well formed.
  • a pressing process of passing the electrode between two rolls heated at high temperature and compressing the electrode to a desired thickness can be performed.
  • the pressing process is not particularly limited in the present invention, and a known pressing process is available.
  • the pressing process is carried out by passing between rotating rolls or by using a flat press machine.
  • n in the expression 'PEO n -lithium salt' represents the number of moles of PEO corresponding to 1 mole of Li of the lithium salt and X in the expression 'PEO n -lithium salt-X' means that it is bridged into a semi-IPN structure.
  • a Li symmetric cell was prepared by applying the PEO 5 -LiFSI membrane of Preparation Example 1 to the surface of lithium metal and applying the PEO 20 -LiFSI-X membrane of Preparation Example 3 therebetween.
  • a Li symmetric cell was prepared by applying the PEO 20 -LiFSI-X membrane of Preparation Example 3 between lithium metals.
  • the resistances of the lithium symmetric cells of Example 1 and Comparative Example 1 and the all-solid batteries of Examples 3 and 4 and Comparative Example 4 were measured by electrochemical impedance spectroscopy (EIS), and the interfacial resistances were confirmed by the points where the semicircular lines in the graph of FIG. 1 and FIG. 2 thus obtained meet the x axis.
  • the interfacial resistances are shown in table 2 below. Table 2 Item Symmetric cell All-solid battery Example 1 Comparative Example 1 Example 3 -Example 4 Comparative Example 4 interfacial resistance ( ⁇ ) 130 350 200 350 2200
  • the resistance of the all-solid battery to which PEO 2 -LiFSI and PEO 20 -LiFSI were sequentially applied based on lithium negative electrode which is Example 3
  • the resistance of the all-solid battery to which PEO 20 -LiFSI and PEO 5 -LiFSI were sequentially applied based on lithium negative electrode which is Example 4 in which the positions of the first polymer and the second polymer were changed, was found to be 350 ⁇
  • the resistance of the all-solid battery to which PEO 12 -LiFSI and PEO 20 -LiFSI were sequentially applied based on the lithium negative electrode, which is Comparative Example 4 using only the second polymer was found to be 2200 ⁇ .
  • the interfacial resistance of the battery in which the first polymer electrolyte layer is placed facing the lithium based on the lithium negative electrode and the second polymer electrolyte layer is placed on top of it is lower, and it can be seen that the interfacial resistance of the battery using the first polymer electrolyte layer and the second polymer electrolyte layer at the same time is lower than that of the battery using only the second polymer electrolyte layer.

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Claims (11)

  1. Electrolyte polymère à structure multicouche pour la batterie tout solide, comprenant :
    une première couche d'électrolyte polymère présentant un rapport molaire EO:Li de polymère à base de poly(oxyde d'éthylène) et de sel de lithium compris entre 1:1 et 7:1; et
    une seconde couche d'électrolyte polymère présentant un rapport molaire EO:Li de polymère à base de poly(oxyde d'éthylène) et de sel de lithium compris entre 8:1 et 30:1.
  2. Électrolyte polymère à structure multicouche pour la batterie tout solide selon la revendication 1, caractérisé en ce que l'épaisseur de la première couche d'électrolyte polymère est comprise entre 1 et 5 µm.
  3. Électrolyte polymère à structure multicouche pour la batterie tout solide selon la revendication 1, caractérisé en ce que l'épaisseur de la seconde couche d'électrolyte polymère est comprise entre 5 et 50 µm.
  4. Électrolyte polymère à structure multicouche pour la batterie tout solide selon la revendication 1, caractérisé en ce que le poids moléculaire moyen en poids du polymère à base de poly(oxyde d'éthylène) est compris entre 1000 000 et 8 000 000.
  5. Électrolyte polymère à structure multicouche pour la batterie tout solide selon la revendication 1, caractérisé en ce que le sel de lithium comprend un choisi dans le groupe constitué de LiCI, LiBr, LiI, LiClO4, LiBF4, LiB10Cl10, LiPF6, LiCF3SO3, LiCF3CO2, LiAsF6, LiSbF6, LiAlCl4, CH3SO3Li, CF3SO3Li, LiSCN, LiC(CF3SO2)3, (CF3SO2)2NLi, (FSO2)2NLi, lithium de chloroborane, carboxylate aliphatique inférieur de lithium, tétraphénylborate de lithium, imide de lithium et des combinaisons de ceux-ci.
  6. Électrolyte polymère à structure multicouche pour la batterie tout solide selon la revendication 1, caractérisé en ce que la seconde couche d'électrolyte polymère est réticulée par un monomère de réticulation pour former des réseaux de polymères semi-interpénétrant.
  7. Électrolyte polymère à structure multicouche pour la batterie tout solide selon la revendication 6, caractérisé en ce que le monomère de réticulation comprend des unités répétitives -(CH2-CH2-O)-.
  8. Électrolyte polymère à structure multicouche pour la batterie tout solide selon la revendication 7, caractérisé en ce que le monomère de réticulation contient de deux à huit liaisons insaturées alkyléniques aux terminaisons.
  9. Électrolyte polymère à structure multicouche pour la batterie tout solide selon la revendication 6, caractérisé en ce que le monomère de réticulation est contenu en une quantité de 5 à 50 % en poids par rapport au polymère à base de poly(oxyde d'éthylène) et au sel de lithium.
  10. Batterie tout solide comprenant une électrode positive, une électrode négative et un électrolyte polymère solide interposé entre elles, qui est caractérisée en ce que l'électrolyte polymère solide est l'électrolyte polymère selon l'une quelconque des revendications 1 à 9.
  11. Batterie tout solide selon la revendication 10, caractérisée en ce que la première couche d'électrolyte polymère est disposée en regard de l'électrode négative.
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CN107636880B (zh) 2020-07-10
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